JP4789663B2 - Thermosetting composition and film provided with a layer obtained from the composition - Google Patents

Description

  The present invention relates to a thermosetting composition, and more particularly to a thermosetting composition containing a resin that is thermally deformed in a specific temperature range as a main agent and giving a cured product without voids.

  A semiconductor device usually includes a step of adhering and fixing a large-diameter silicon wafer to a dicing mount for wafer dicing, a dicing step of cutting the fixed silicon wafer into a semiconductor chip, and processing the semiconductor A step of peeling and separating the chip from the dicing tape, and a step of bonding and fixing the semiconductor chip to the lead frame using a curable liquid adhesive (usually referred to as a die bond agent). It is manufactured through a process.

  Recently, in order to simplify the process and to avoid problems such as contamination of semiconductor parts due to liquid components when using liquid adhesive, the function of a dicing tape for fixing silicon wafers and semiconductor chips A dicing / die bonding adhesive sheet having a function as a die bonding agent for adhering and fixing to a lead frame is used.

  In the dicing process, the dicing / die bonding adhesive sheet needs to be able to securely adhere and hold so that the silicon wafer is not peeled off from the dicing mount. Further, when separating the semiconductor chip, it is necessary to separate from the dicing mount together with the semiconductor chip. Next, in the die-bonding step, the film-like material needs to have sufficient adhesive strength to crimp and fix the semiconductor chip on the lead frame. It is necessary to have the ability to firmly bond and fix to the lead frame.

  As a sheet for dicing die bonding, an adhesive composition containing a polyimide resin is proposed in JP-A-9-67558 (Patent Document 1), but the polyimide resin has a high Tg and a high elastic modulus. It has been insufficient to relieve the thermal stress between the semiconductor component and the adhesive substrate, and has been unreliable.

  Silicone adhesives having lower Tg and elastic modulus and exhibiting both adhesive properties and thermosetting properties are also known (Patent Documents 2 to 4). These are room temperature curable products that are crosslinked and cured by moisture and moisture in the air, and have a long period of several days to several weeks until a desired large adhesive force is obtained. As a pressure-sensitive adhesive for dicing and a pressure-sensitive adhesive for die bonding, there are problems in terms of productivity.

Moreover, as a silicone-based adhesive that does not generate voids during thermal curing, an organopolysiloxane composition that cures by both peroxide curing and hydrosilylation curing is known (Patent Document 5).
JP-A-9-67558 JP 7-53871 A JP 7-53942 A JP-A-7-70541 JP 2005-53966 A

However, the organopolysiloxane composition can be bonded to a substrate at a lower pressure so that the chip does not break due to the recent low-pressure die attach property, that is, the semiconductor chip is thinner. Not satisfactory in terms. Therefore, an object of the present invention is to provide an adhesive composition that is pressure-bonded at a low pressure to give a cured product having no voids.

That is, the present invention is as follows.
(A) Organopolysiloxane resin represented by the following average composition formula (1), which is solid at normal temperature and has a weight average molecular weight (in terms of styrene) of 400 to 10,000
[Chemical 1]
R ¹ _m R ² _n R ³ _k SiO _{(4-mnk) / 2} (1)

(In Formula (1), R ¹ is a phenyl group, R ³ is an alkenyl group, R ² is a monovalent group excluding a phenyl group and an alkenyl group, and m, k, and n are each 0.45 ≦ m ≦ 2.78, 0 <k ≦ 0.5, 0.2 ≦ n ≦ 2.5, provided that 0.9 ≦ (m + n + k) ≦ 2.8)
(B) Organic peroxide having a half-life of 10 hours and a temperature of 90 ° C or higher
(C) an organohydrogenpolysiloxane having at least two SiH bonds in one molecule, and
(D) In a thermosetting composition comprising an addition reaction catalyst ,
(A) organopolysiloxane having at least two alkenyl groups in one molecule, a composition of 50% to 99% of the substituents the total number attached to the silicon atom, wherein the Ru der phenyl group .

  The composition of the present invention becomes flexible and deforms before thermosetting, and becomes a shape conforming to the shape of the substrate surface to which the composition is applied, so that the bubbles are cured while trapped. It is possible to form a cured product free from voids.

The organopolysiloxane resin (A) in the composition of the present invention contains at least two or more alkenyl groups in one molecule, and 10% or more of the total number of substituents bonded to silicon atoms is a phenyl group, It is characterized by being thermally deformed at a temperature of 30 ° C. or higher and lower than the thermosetting start temperature of the composition. Examples of the organopolysiloxane resin (A) include those represented by the following average composition formula (1).

R ¹ _m R ² _n R ³ _k SiO _{(4-mnk) / 2} (1)

In formula (1), R ¹ is a phenyl group, R ³ is an alkenyl group, and R ² is a monovalent group excluding the phenyl group and the alkenyl group. 10% to 99% of the total substituents are phenyl groups, that is, 0.1 ≦ m / (m + n + k) ≦ 0.99.

The organopolysiloxane resin (A) is thermally deformed at a temperature of 30 ° C. or higher and lower than the thermosetting start temperature of the composition. That is, it becomes flexible once before thermosetting and the shape is deformed, and further tackiness appears. Therefore, for example, when applied on a substrate on which wiring is formed, the shape tends to follow the undulation of the wiring, and bubbles hardly remain in the cured product. In the present invention, the thermal deformation was measured by placing a small amount of organopolysiloxane on a hot plate and gradually increasing the temperature while visually observing the temperature at which the shape of the organopolysiloxane changes. . Further, the thermosetting start temperature is measured as a start temperature of the thermosetting reaction in the differential thermal analysis measurement, for example, as shown in FIG. 150 ° C.

The organopolysiloxane resin (A) is solid at room temperature, and preferably has a weight average molecular weight (in terms of styrene) of 400 to 10,000, more preferably 600 to 10,000. Preferably, in the above formula (1), 0.9 ≦ m + n + k ≦ 2.8, and more preferably 1.1 ≦ m + n + k ≦ 2.6. Therefore, m is preferably 0.09 (= 0.9 × 0.1) ≦ m ≦ 2.78 (= 2.8 × 0.99), more preferably 0.15 ≦ m ≦ 1. 4. It is difficult for the organopolysiloxane having m less than the lower limit to have the above heat deformability. On the other hand, organopolysiloxanes in which m exceeds the upper limit value have a too high heat deformation temperature, resulting in insufficient low-pressure die attachability.

In the formula (1), k representing the amount of the alkenyl group (R ³ ) is 0 <k ≦ 0.5, preferably 0.05 ≦ k ≦ 0.3. However, it is necessary that there are at least two alkenyl groups in one molecule. As the alkenyl group, an alkenyl group having 2 to 6 carbon atoms such as a vinyl group, an allyl group, and a butenyl group is preferable, and among them, a vinyl group is industrially preferable.

R ² is a monovalent group excluding a phenyl group and an alkenyl group, such as a hydrogen atom, a hydroxyl group, or a hydrocarbon group. Preferred hydrocarbon groups are those having 1 to 6 carbon atoms, more preferably alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl and 1 to 6 carbon atoms. 4 of which the methyl group is particularly preferable. N in the formula (1) is preferably 0.2 ≦ n ≦ 2.5, more preferably 0.5 ≦ n ≦ 2.1.

  The organopolysiloxane resin (A) may be a mixture of two or more kinds of organopolysiloxanes. Further, the molecule may have a branched structure, that is, a T unit and / or a Q unit described later.

  The organopolysiloxane resin (A) can be produced by a conventionally known method. For example, according to the structure of the desired organopolysiloxane resin, the corresponding organochlorosilanes may be cohydrolyzed, optionally in the presence of an alcohol having 1 to 4 carbon atoms, to remove by-product hydrochloric acid and low-boiling components. Obtainable. In addition, when starting from silanes having an organic residue such as phenyl group or methyl group in the molecule, silicone oil, or cyclic siloxane, an acid catalyst such as hydrochloric acid, sulfuric acid, methanesulfonic acid, etc. is used, In some cases, water for hydrolysis is added to advance the polymerization reaction, and then the acid catalyst and low-boiling components used are similarly removed to obtain the desired organopolysiloxane.

  In the present invention, the (B) curing catalyst is a catalyst for polymerizing the alkenyl group of the organopolysiloxane resin (A), and an organic peroxide is preferable. Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, t-butyl benzoate, t-butyl peroxybenzoate, di-t-butyl peroxide, di-t-hexyl peroxide, and t-butyl cumi Ruperoxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 1,6-bis ( t-butylperoxycarboxy) hexane, di- (4-methylbenzoyl) peroxide, di- (2-methylbenzoyl) peroxide, t-butylperoxyisopropylmonocarbonate, di- (2-t-butylperoxyisopropyl) Benzene and the like can be exemplified. Preferably, those having a half-life of 10 hours and a temperature of 90 ° C. or higher, more preferably 110 ° C. or higher are used. Examples of such peroxides include dicumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-bis (t -Butylperoxy) hexane, di- (2-t-butylperoxyisopropyl) benzene.

  The compounding amount of the organic peroxide is a catalytic amount, typically 0.1 to 20 parts by mass, more typically 0.2 to 15 parts by mass with respect to 100 parts by mass of the organopolysiloxane (A). Part, most typically about 0.5 to 10 parts by weight. If it is less than the lower limit value, sufficient crosslinking cannot be obtained, and even if the upper limit value is exceeded, it is difficult to obtain performance improvements that meet the cost increase.

  The composition of the present invention containing the (A) organopolysiloxane resin and (B) the curing catalyst is thermally cured, and the glass transition point Tg of the cured product is 120 ° C. or less. The temperature is significantly lower than that of the conventional polyimide composition, and the thermal stress can be relaxed.

The compositions of the present invention may contain further (C) an organohydrogenpolysiloxane and (D) an addition reaction catalyst, in which case, in addition to the above polymerization reaction (C) an organohydrogenpolysiloxane (A) Cured by addition reaction with organopolysiloxane. The (C) an organohydrogenpolysiloxane, linear, cyclic, branched, it can be used as a three-dimensional network structure. There are 2 or more, preferably 3 or more, more preferably 2 to 500, and most preferably 3 to 100 SiH groups in one molecule. The organohydrogenpolysiloxane (C) is, for example, represented by the following average composition formula (2).

R ⁴ _a H _b SiO _{(4-ab) / 2} (2)

In the above formula (2), R ⁴ is a hydrocarbon group excluding an aliphatic unsaturated bond, preferably a hydrocarbon group having 1 to 10 carbon atoms. For example, alkyl such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group; phenyl Aryl groups such as a group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as a benzyl group, a phenylethyl group and a phenylpropyl group; and a part or all of hydrogen atoms of these groups are fluorine, bromine, chlorine, etc. And the like, for example, chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group and the like. Of these, an alkyl group and an aryl group are preferable, and a methyl group and a phenyl group are more preferable. For example, methyl hydrogen polysiloxane, dimethyl siloxane / methyl hydrogen siloxane copolymer, and dimethyl siloxane / methyl hydrogen siloxane / methyl phenyl siloxane copolymer, those having both ends of a trimethylsiloxy group, and molecular chains Those that are dimethylhydrogensiloxy groups at both ends are used.

Preferably, a is 0.7 to 2.1, b is 0.001 to 1.0, and a + b is 0.8 to 3.0, more preferably a is 1.0 to 2.0, b Is 0.01 to 1.0, and a + b is 1.5 to 2.5.

The SiH group may be located at either the molecular chain end or in the middle of the molecular chain, or may be located at both of them. (C) organohydrogenpolysiloxane, from the viewpoint of handling of the composition, preferably a polymerization degree (number of silicon atoms) is 2 to 1,000, more preferably 3 to 300, and most preferably 4 About 150 pieces. Further, the viscosity at 25 ° C. is preferably 0.1 to 5,000 mPa · s, more preferably 0.5 to 1,000 mPa · s, most preferably about 5 to 500 mPa · s at room temperature (25 ° C.). A liquid one is used.

In the composition of the present invention, the amount of organohydrogenpolysiloxane (C) is such that the molar ratio (H / Vi) of SiH groups in the molecule to alkenyl groups in (A) organopolysiloxane resin is 0.01. It is -0.7 mol / mol, Preferably it is 0.05-0.5. The composition exhibits high adhesiveness when the alkenyl group and SiH group react with each other, and is suitably used for a dicing tape that does not cause chip position shift or chip jump during the dicing process. When H / Vi is out of the above range, it is difficult to achieve such viscosity.

(D) Examples of the addition reaction catalyst include platinum, palladium, rhodium, and compounds thereof such as chloroplatinic acid, alcohol-modified chloroplatinic acid, coordination compounds of chloroplatinic acid and olefins, vinylsiloxane or acetylene compounds, tetrakis (Triphenylphosphine) palladium and chlorotris (triphenylphosphine) rhodium are used, and platinum compounds are preferred.

(D) The compounding amount of the addition reaction catalyst is typically 1 to 500 ppm, more preferably 10 to 100 ppm as the amount of the catalytic metal element with respect to the total weight of the composition.

  The composition of the present invention may contain an inorganic filler. Examples of inorganic fillers include finely divided silica, crystalline silica, calcined spherical silica, hollow filler, silsesquioxane, fumed titanium dioxide, magnesium oxide, zinc oxide, iron oxide, aluminum hydroxide, magnesium carbonate, calcium carbonate Inorganic fillers such as zinc carbonate, layered mica, carbon black, diatomaceous earth, and glass fibers, and organosilicon compounds such as organoalkoxysilane compounds, organochlorosilane compounds, organosilazane compounds, and low molecular weight siloxane compounds. And the like and the like surface-treated filler. Moreover, silicone rubber powder, silicone resin powder, etc. are mentioned. In particular, fine powder silica, crystalline silica, calcined spherical silica, silicone rubber powder, silicone resin powder, and the like are effective in reducing the volume expansion coefficient and preventing warpage of the semiconductor package.

Particularly preferred are finely divided silica, preferably a specific surface area (BET method) is 50 m ² / g or more, more preferably 10 to 400 m ² / g, particularly preferably 50 to 300 m ² / g. The finely divided silica may be one conventionally used as a reinforcing filler for silicone rubber, and includes, for example, precipitated silica, fumed silica, calcined silica, etc. Good. Fine powder silica may be used as it is, but for good fluidity, silazanes such as hexamethyldisilazane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxy. Silane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, vinyltris (methoxyethoxy) silane, trimethylchlorosilane, dimethyldichlorosilane, divinyldimethoxysilane and chloropropyltrimethoxy Surface treatment with silane coupling agent such as silane, organosilicon compound such as polymethylsiloxane, organohydrogenpolysiloxane, etc. to make it hydrophobic. It is preferred.

  As a compounding quantity of an inorganic filler, it is 1-50 mass parts with respect to 100 mass parts of (A) organopolysiloxane resin, and it is preferable to set it as 1-30 mass parts.

  When using the composition of this invention as an adhesive agent, it is preferable to mix | blend (E) adhesiveness imparting component. The component is preferably one or more selected from organic compounds, organic silicon compounds, and organic titanium compounds containing at least one, preferably two or more, predetermined functional groups.

  Examples of the organosilicon compound include alkenyl groups such as vinyl group and allyl group; epoxy groups such as γ-glycidoxypropyl group and β- (3,4-epoxycyclohexyl) ethyl group; γ-acryloxypropyl Group, (meth) acryloxy group such as γ-methacryloxypropyl group; alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group; alkoxysilyl such as trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group Group: an organosilane having a functional group selected from an isocyanate group and an SiH group, preferably two or more, and a siloxane oligomer having a linear or cyclic structure having 3 to 50, particularly 5 to 20, silicon, triallyl isocyan Nurate (alkoxy) silyl modified products and their siloxane derivatives It is below. For example, the following silicon compounds are mentioned.

  Examples of the organic titanium compounds include tetra-i-propyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetrastearyl titanate, triethanolamine titanate, titanium acetylacetonate, titanium ethyl acetoacetate, titanium lactate and octylene glycol titanate. , Isopropyl tristearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, tetrabutoxy titanium, tetrakis (2-ethylhexyl) Oxy) titanium, tetrastearyloxytitanium, Data pyridinium stearate, tetra octyloxy titanium, titanium -i- propoxy octylene glycolate, titanium ethyl acetonate, titanium lacto sulfonates, or those condensation reaction product oligomers, polymers, and the like.

  Examples of organic compounds include organic compounds having at least one alkenyl group and ester group in the molecule, such as allyl esters of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and vinyl acetic acid, benzoic acid allyl ester, and phthalic acid. Examples include allyl esters such as acid diallyl ester, pyromellitic acid tetraallyl ester, and alkyl acid allyl ester.

Moreover, the organic compound or organosilicon compound which contains a phenylene skeleton in the molecule | numerators shown below, and has at least 2 functional group chosen from an epoxy group, an alkenyl group, and a hydroxyl group is mentioned.

（Ｒは水素原子又は炭素数１〜３のアルキル基、ｍは０又は１〜１６の整数である。）

(R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m is 0 or an integer of 1 to 16)

（ｎは１〜４である。）

(N is 1-4)

（ｎは１〜４、ｐは２〜３０、Ｒ¹は水素原子又は炭素数１〜３のアルキル基である。）

(N is 1 to 4, p is 2 to 30, and R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

Ｒ_w，Ｒ_xは一価炭化水素基であり、ｑ＝１〜５０、ｈ＝０〜１００、好ましくはｑ＝１〜２０、ｈ＝１〜５０であり、
Ｒ''は下記のいずれかであり、

R _w and R _x are monovalent hydrocarbon groups, q = 1 to 50, h = 0 to 100, preferably q = 1 to 20, h = 1 to 50,
R '' is one of the following:

Ｒ_w，Ｒ_xは上記と同様であり、ｙ＝０〜１００である。］

R _w and R _x are the same as described above, and y = 0 to 100. ]

  Furthermore, an alkoxysilyl group such as trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, acrylic group, methacryl group, ester group, anhydrous carboxy group, isocyanate group, amino group, amide group, etc. were introduced into the above compound. Things can also be used.

In addition, as said _Rw , _Rx , a C1-C12, especially 1-8 thing is preferable, and an alkyl group, an aryl group, an aralkyl group, an alkenyl group etc. are mentioned, An alkoxy group, an acryl group, methacryl And those in which those hydrogen atoms are substituted with a group, an acryloyl group, a methacryloyl group, an amino group, an alkylamino group and the like.

  In addition, when using the compound which has an epoxy group as (E) adhesiveness imparting component, it is preferable that the epoxy equivalent of this compound is 100-5,000 g / mol, especially 150-3,000 g / mol. If the epoxy equivalent is too small, the tackiness may be lowered, and if too large, the adhesiveness may be lowered. Moreover, you may use together an organometallic chelate, an amine compound, an amide compound, an imidazole compound, an acid anhydride etc. as a ring-opening catalyst of this epoxy compound.

  (E) The compounding amount of the adhesion-imparting component is 0.1 to 20 parts per 100 parts by mass of (A) organopolysiloxane resin and (C) organohydrogenpolysiloxane when used. It is a mass part, Preferably it is 0.5-15 mass parts. If the blending amount is too small, sufficient adhesive force necessary for the present invention cannot be obtained, and if the blending amount is too large, the cost becomes high, which is uneconomical.

Moreover, in order to improve adhesiveness, the composition of this invention may contain (F) organopolysiloxane resin. Here, “resin” means a material that is semi-solid or solid at room temperature. The organopolysiloxane resist increases the tackiness and transferability of the adhesive sheet of the present invention depending on the type of substrate such as a wafer or die frame.

The component (F) includes a unit represented by R ⁵ ₃ SiO _1/2 (hereinafter referred to as “M unit”) and a SiO ₂ unit (hereinafter referred to as “Q unit”). An organopolysiloxane resin or a mixture thereof containing both units in a ratio such that the molar ratio of Q units is 0.6 to 1.7, preferably 0.6 to 1.0. The molar ratio is less than the above lower limit, it may adhesive strength and tackiness of the adhesive film of the present invention is reduced, also the adhesive strength exceeds the upper limit to the contrary is poor, an adhesive object Holding force may decrease. R ⁵ is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group; Examples thereof include a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an alkenyl group such as a vinyl group, an allyl group, and a hexenyl group. Among these, a methyl group is preferable.

(F) The organopolysiloxane resin may have a hydroxyl group (silanol group) bonded to a silicon atom. The content of the hydroxyl group is preferably about 0.02 to 0.05 mol% of the total molar amount of the group bonded to the silicon atom of (F) organopolysiloxane resin. When the content exceeds the above amount, the thermosetting property of the composition of the present invention may be lowered, which is not preferable.

The organopolysiloxane resin (F) is a trifunctional unit represented by R ⁵ SiO _3/2 and / or a bifunctional represented by R ⁵ ₂ SiO within a range not impairing the object and effect of the present invention. It may have a relatively small amount of units (wherein R ⁵ is the same as above).

Preferred (F) organopolysiloxane resin is an organopolysiloxane having (CH ₃ ) ₃ SiO _1/2 units / SiO ₂ units of 1 / 0.75 (mol / mol) and containing about 1 mol% of hydroxyl groups. Resin is mentioned.

Furthermore, the composition of this invention may contain organopolysiloxane different from the said (A) component and (F) component. The organopolysiloxane contains an alkenyl group bonded to two or more silicon atoms on average in one molecule, and may include those represented by the following formula.
R ⁶ _a SiO _{(4-a) / 2}
(In the formula, R ⁶ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, but is 1.0 × 10 ⁻⁵ mol%, preferably 1.0 × 10 ⁻⁴ mol, of R ^6. %, More preferably 0.01 mol% or more and 20 mol% or less, particularly 10 mol% or less is an alkenyl group, and a is a number of 1.5 to 2.8.)

R ⁶ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group and other alkyl groups; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, Examples include alkenyl groups such as xenyl group, cyclohexenyl group, and octenyl group.

  Furthermore, organic solvents, creep hardening inhibitors, plasticizers, thixotropic agents, pigments, dyes, fungicides and the like can be blended as other optional components within the range not impairing the object of the present invention. When the composition of the present invention is applied on a film, it is preferably diluted with an organic solvent. Examples of the organic solvent include toluene, xylene, hexane, heptane, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, and the like. When this organic solvent is used, the amount used may be adjusted according to the desired viscosity of the resulting dilution, etc., but typically from 20 to 90 parts per 100 parts by weight of the total composition. Part by weight, more typically about 30 to 80 parts by weight.

  Moreover, when the composition of this invention contains (D) addition reaction catalyst, it can contain the control agent compound which has the reaction inhibitory effect with respect to (D) addition reaction catalyst. Such compounds include phosphorus-containing compounds such as triphenylphosphine, nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole, sulfur-containing compounds, acetylenic compounds, compounds containing two or more alkenyl groups, hydroper Examples include oxy compounds and maleic acid derivatives. Since the degree of the reaction delay effect varies greatly depending on the chemical structure of the control agent compound, it is necessary to adjust the amount of the control agent compound to be used and adjust it to an optimum amount.

  The composition of the present invention can be prepared by mixing the above components. It can also be produced by heating and mixing the silicone component and the inorganic filler and then adding other components and mixing at room temperature. The obtained composition can be used as a pressure-sensitive adhesive in an uncured state or in a state after the addition reaction when it also includes the components (C) and (D), and has good adhesion to various substrates. Showing gender. For example, in a dicing process when manufacturing a semiconductor device, it is applied to a dicing mount and used as an adhesive material for temporary fixing for fixing a silicon wafer.

  Moreover, this invention composition can be used as an adhesive agent which gives the hardened | cured material which has a strong adhesive force by heat-processing. For example, in the die-bonding process when manufacturing a semiconductor device, the semiconductor chip integrally having an adhesive layer made of an uncured adhesive is pressure-bonded to a lead frame and then subjected to heat treatment, whereby the present invention A semiconductor device in which the base material and the semiconductor chip are firmly bonded can be manufactured through the cured layer of the adhesive. Subsequent to the dicing process in the semiconductor manufacturing process, it can be used in a die bonding process.

  When the composition of the present invention is used as a thermosetting adhesive, the adhesive is applied onto a target substrate, and when the adhesive contains a volatile solvent, the adhesive is dried. The solvent and the like are removed, and an adhesive layer is formed to a predetermined thickness. Another substrate is pressure-bonded and fixed to the adhesive layer. The fixed substrate is subjected to a required process such as cutting. If necessary, a heat-treated adhesive layer is formed on the spot or in another process by heat treatment.

  The composition of the present invention can be applied on a film substrate and used as an adhesive film. As the film substrate, films such as polyethylene, polypropylene, polyester, polyamide, polyimide, polyamideimide, polyetherimide, polytetrafluoroethylene, paper, metal foil, and the like can be used. Moreover, in order to improve the transferability of the pressure-sensitive adhesive / adhesive layer in the pickup process, the base film may be surface-treated with a release agent.

  Next, the composition of the present invention is applied onto a film, and when the composition contains a volatile solvent or the like, the layer is formed by drying to remove the solvent or the like. There is no restriction | limiting in particular in the thickness of this layer, Although it can set according to the objective, Typically, it is about 0.01-2.0 mm. Next, when the layer also contains the components (C) and (D), the layer is heat-treated at a temperature at which addition reaction occurs but thermosetting does not occur to form an adhesive layer. If necessary, a peelable film may be further pressure-bonded onto the pressure-sensitive adhesive layer to form a three-layer structure. The film can be rolled up in the form of a long tape to improve workability.

When the film has a two-layer structure, after the pressure-sensitive adhesive layer is pressure-bonded to the target substrate, the peelable substrate film is removed, and the adherend is pressure-bonded and fixed to the exposed pressure-sensitive adhesive surface. In the case of a three-layer structure, the peelable film on one side is removed, and after the adhesive layer is pressure-bonded to the target substrate, the peelable film on the other surface is removed, and the exposed adhesive surface is Crimp and fix the adherend. Thereafter, the adherend is fixed by heating.

  The drying conditions for the solvent in the composition are usually 2 hours or more at room temperature, 1 to 20 minutes at 40 to 130 ° C, and preferably 1 to 20 minutes at 50 to 120 ° C. In some cases, the reaction may proceed simultaneously with the addition reaction, but it is necessary to set the temperature within such a range that organic peroxide curing does not occur.

  Further, as the bonding conditions, (B) the curing catalyst effectively exhibits curing performance, usually at 100 to 250 ° C. for 15 to 60 minutes, particularly preferably at 120 to 230 ° C. for 15 to 60 minutes. is there.

  Examples of the substrate on which the composition of the present invention can be adhered and adhered include metals such as Fe, Al, Cr, Ni, Si, Cu, Ag, and Au; inorganic substances such as glass, silicon nitride, and silicon carbide, or ceramics A substrate such as an organic material such as epoxy resin, bakelite, polyimide, polyamide, polyester, or silicone resin.

  A highly reliable semiconductor device can be manufactured with high productivity by using the above-described film, particularly a film having a three-layer structure, in a dicing process and a die bonding process. First, a dicing mount is prepared in which the surface on the side on which the silicon wafer is mounted has sufficient adhesiveness. The base material of the film is adhered and fixed on the dicing mount. In the case of a three-layer structure, the base film on the side not adhered to the dicing mount is then peeled off and removed. Next, a silicon wafer is stacked on the exposed adhesive layer and fixed by pressing. Thereafter, the silicon wafer is diced and cut and processed so that semiconductor chips individually separated from the silicon wafer are obtained. After the dicing is completed, the obtained semiconductor chips are individually separated and taken out. At this time, the adhesive layer is easily peeled off from the peelable film on the dicing mount surface and taken out integrally with the semiconductor chip. In this way, a semiconductor chip having an adhesive layer on one side can be obtained.

  Subsequently, the semiconductor chip is pressure-bonded to the prepared lead frame via the adhesive layer, and is adhered and fixed. Finally, the structure including the semiconductor chip, the adhesive layer, and the lead frame is subjected to a required heat treatment, the adhesive layer is cured, and the semiconductor chip is bonded to the lead frame. In this manner, a semiconductor device in which the base material and the semiconductor chip are firmly bonded via the cured layer of the adhesive of the present invention can be manufactured with high productivity.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In addition, a part shows a mass part by the following example, and a viscosity is a value of 25 degreeC.

Adhesion imparting components (i) to (vi) used in the following examples are as follows.

接着付与成分（ｉｖ）ＫＢＥ9007（イソシアネートシラン：信越化学工業（株）商品名）
接着付与成分（ｖ）

Adhesion imparting component (iv) KBE9007 (isocyanate silane: Shin-Etsu Chemical Co., Ltd. trade name)
Adhesion imparting component (v)

接着付与成分（ｖｉ）

Adhesion imparting component (vi)

[Example 1]
70 parts of an organopolysiloxane resin represented by the following average composition formula and having a heat distortion temperature of 40 ° C.,
(C ₆ H ₅ ) _0.9 (CH ₃ ) _0.2 (CH ₂ ═CH) _0.2 SiO _1.35
20 parts of hydrophobic silica having a specific surface area of 120 m ² / g treated with trimethylsilyl groups,
Dimethylsiloxane / methylhydrogensiloxane copolymer having SiH bonds at both molecular chain ends and molecular chain side chains (viscosity 12 mPa · s, SiH bond content 0.54 mass%) H / Vi = 0.3 mol / mol The amount of chloroplatinic acid and divinyltetramethyldisiloxane complex as platinum metal, 30 ppm with respect to the total amount of the composition,
This composition was prepared by mixing 5 parts of di- (2-t-butylperoxyisopropyl) benzene with 100 parts of the organopolysiloxane, 1.5 parts of the adhesion-imparting agent (i), and 1-ethynylcyclohexanol. Was dissolved in toluene so as to be 30% by weight to obtain a composition. The amount of 1-ethynylcyclohexanol was such that the addition reaction was substantially completed in 10 minutes at 80 ° C. (the same applies hereinafter). When the glass transition temperature of the cured product obtained by curing the composition at 170 ° C. for 60 minutes was measured by a volume expansion coefficient (tensile type) using a viscoelastic device, it was 46 ° C.

[Example 2]
An organopolysiloxane resin represented by the following average composition formula and having a heat distortion temperature of 53 ° C.

(C ₆ H ₅ ) _0.89 (CH ₃ ) _0.28 (CH _{2 ═CH} ) _0.28 SiO _1.28

A composition was prepared in the same manner as in Example 1 except that (ii) was used as an adhesion-imparting agent, and the Tg was measured in the same manner.

[Example 3]
An organopolysiloxane resin represented by the following average composition formula and having a heat distortion temperature of 47 ° C:

(C ₆ H ₅ ) _1.10 (CH ₃ ) _0.25 (CH ₂ ═CH) _0.05 SiO _1.30

A composition was prepared in the same manner as in Example 1 except that (iii) was used as an adhesiveness-imparting agent, and Tg was measured in the same manner.

[Example 4]
An organopolysiloxane resin represented by the following average composition formula and having a heat distortion temperature of 53 ° C.
(C ₆ H ₅ ) _0.6 (CH ₃ ) _0.35 (CH ₂ ═CH) _0.25 SiO _1.15
As the organohydrogenpolysiloxane, a diphenylsiloxane / dimethylsiloxane / methylhydrogensiloxane copolymer having a silicon atom-bonded hydrogen atom at both molecular chain terminals and molecular chain side chains (viscosity of 12 mPa · s, phenyl content of 30 mol%, A composition was prepared in the same manner as in Example 1 except that the SiH bond content (0.34% by mass) and the adhesion-imparting agent (iv) were used. there were.

[Example 5]
A composition was prepared in the same manner as in Example 4 except that the organopolysiloxane used in Example 2 and (v) was used as the adhesion-imparting agent. Met.

[Example 6]
An organopolysiloxane resin represented by the following average composition formula and having a heat distortion temperature of 55 ° C.
(C ₆ H ₅ ) _0.89 (CH ₃ ) _0.27 (OH) _0.01 (CH _{2 ═CH} ) _0.27 SiO _1.28
Organohydrogenpolysiloxane in an amount of H / Vi = 0.35 mol / mol,
A composition was prepared in the same manner as in Example 4 except that the adhesion-imparting agent (vi) was used, and the Tg was measured in the same manner.

[Example 7]
An organopolysiloxane resin represented by the following average composition formula and having a heat distortion temperature of 55 ° C.
(C ₆ H ₅ ) _1.09 (CH ₃ ) _0.29 (OH) _0.02 (CH ₂ ═CH) _0.27 SiO _1.16
As the organohydrogenpolysiloxane, a diphenylsiloxane / dimethylsiloxane / methylhydrogensiloxane copolymer having a silicon atom-bonded hydrogen atom at both molecular chain terminals and molecular chain side chains (viscosity of 12 mPa · s, phenyl content of 30 mol%, A composition was prepared in the same manner as in Example 6 except that (v) was used as an adhesion promoter, and the Tg was measured in the same manner. there were.

[Example 8]
100 parts of an organopolysiloxane resin represented by the following average composition formula and having a heat distortion temperature of 50 ° C.,
(C ₆ H ₅ ) _0.85 (CH ₃ ) _0.25 (CH ₂ ═CH) _0.05 SiO _1.43
5 parts of di- (2-t-butylperoxyisopropyl) benzene and 1.5 parts of the adhesion-imparting agent (v) are mixed, and this composition is dissolved in toluene so as to be 30% by weight. A product was prepared. The Tg of the cured product obtained by curing the composition at 170 ° C. for 60 minutes was 46 ° C.

[Example 9]
An organopolysiloxane resin represented by the following average composition formula and having a heat distortion temperature of 40 ° C.
(C ₆ H ₅ ) _0.9 (CH ₃ ) _0.2 (CH ₂ ═CH) _0.2 SiO _1.35
A composition was prepared in the same manner as in Example 6 except that Tg was measured in the same manner as in Example 6.

[Comparative Example 1]
Organopolysiloxane represented by the following average composition formula,
(CH ₃ ) _1.17 (CH ₂ = CH) _0.27 SiO _1.28
The composition was prepared in the same manner as in Example 1 except that the adhesion promoter (iii) was used, and the Tg was measured in the same manner.

[Comparative Example 2]
Organopolysiloxane represented by the following average composition formula,
(CH ₃ ) _1.27 (CH ₂ = CH) _0.27 SiO _1.23
The composition was prepared in the same manner as in Comparative Example 1 except that the adhesion promoter (v) was used, and the Tg was measured in the same manner.

[ Example 10 ]
A composition was prepared in the same manner as in Example 2 except that the adhesion-imparting agent (ii) was not added, and Tg was measured in the same manner.

[Comparative Example 3]
70 parts of an oily linear dimethylpolysiloxane having a degree of polymerization of 10,000 at both ends of a molecular chain having a methyl group, a phenyl content of 30 mol% and a vinyl group of 0.005 mol per 100 g;
Organosiloxane containing alkenyl group and phenyl group (C ₆ H ₅ ) _0.6 (CH ₃ ) _1.3 (CH _{2 ═CH} ) _0.13 SiO _0.985 20 parts, specific surface area treated with trimethylsilyl group Diphenylsiloxane / dimethylsiloxane / methylhydrogensiloxane copolymer having 20 m of hydrophobic silica of 120 m ² / g and a silicon atom-bonded hydrogen atom at both ends and side chains of a molecular chain having a viscosity of 12 mPa · s: containing phenyl 30 mol% (silicon atom-bonded hydrogen atom content = 0.34 mass% (H / Vi (ie, the molar ratio of the total SiH groups to the total vinyl groups in the vinyl group-containing organopolysiloxane, and so on)) ) = 0.35 mol / mole), 1-ethynylcyclohexanol, an amount at which the addition reaction is substantially completed in 80 minutes at 80 ° C. , A complex of chloroplatinic acid and divinyltetramethyldisiloxane as platinum metal, 30 ppm with respect to the total amount of the composition, and di- (2-t-butylperoxyisopropyl) benzene in 5 parts with respect to 100 parts of the organopolysiloxane, A composition was prepared by mixing 3 parts of the adhesion-imparting agent (iii) and dissolving the composition in toluene to 30% by weight, and the glass transition point of the cured product was −40 ° C. .

Each of the prepared compositions was applied onto a 50 μm thick PET film coated with a fluorine-containing silicone release agent, left at room temperature for 10 minutes, and then heat-treated at 80 ° C. for 10 minutes to obtain a thickness. An adhesive layer of about 50 μm was formed. By the heat treatment, the composition other than Example 8 was cured by addition reaction. Next, a 300-micron-thick 8-inch wafer was attached to the adhesive layer of the PET film at 60 ° C. and subjected to the following tests.

Each test method is as follows.
A transferable 300-micron-thick 8-inch wafer was cut into 10 mm square with a dicer (manufactured by Disco), and when picked up, A was transferred to the adhesive layer, and B was not.
Chip position deviation After cutting a 300-micron thick 8-inch wafer into a 10 mm square with a dicer (manufactured by Disco), the wafer is rotated at 3000 rpm, and air blowing and water washing are performed for 5 minutes. One was A and the other was B.
Chip skipping A chip misalignment test where no chip skipping occurred after cleaning was designated as A, and those other than that were designated as B.
Adhesiveness
It was attached by (10 × 25mm) on the end of the SUS test piece of width 25mm in viscosity adhesive layer. Next, the base PET film is peeled off, and a UV curable solder resist (trade name: PSR4000 AUS308, manufactured by Taiyo Ink Manufacturing) layer is formed on the BT resin on the exposed adhesive surface. Overlap the edge of the substrate, sandwich the adhesive layer, and test by applying a weight of 2000g to the part where the end of the SUS test piece, adhesive layer and unit substrate are laminated for 1 minute. Got the body. Then, it was placed in a heating furnace and heated at 170 ° C. for 60 minutes to cure the adhesive layer. Thereafter, the bonded specimen was measured for shear adhesive strength (kg / cm ² ) using a shear adhesive strength measuring device in accordance with JIS K6850.
Adhesion durability The bonded specimens were stored at 80C and 90% RH for 7 days and then subjected to a shear test in the same manner.
The wafer is cleaved in the heat-deformable transfer test, and die attachment on the unit substrate, placing the substrate board onto a hot plate at 120 ° C., and the load pressure of 0.1MPa from the top of the wafer, the adhesive layer The heat deformability was observed visually. Next, the temperature of the hot plate was set to 170 ° C. to cure the adhesive. After cooling the obtained cured product to room temperature, the presence or absence of voids was examined using an ultrasonic flaw detector. The sample that was thermally deformed and had no voids was designated A, and the other sample was designated B.

表１に示すように、本発明の組成物は、軟化性に優れボイドの無い硬化物を与えた。これに対して、比較例の組成物は軟化することなく硬化して、得られた硬化物内部にボイドが観察された。さらに、本発明の組成物は、硬化後の接着性にも優れた。実施例１０は、接着付与成分を含まないので、接着力は弱いが粘着剤としては有用である。

As shown in Table 1, the composition of the present invention gave a cured product having excellent softening properties and no voids. On the other hand, the composition of the comparative example was cured without softening, and voids were observed inside the obtained cured product. Furthermore, the composition of this invention was excellent also in the adhesiveness after hardening. Since Example 10 does not contain an adhesion-imparting component, the adhesive strength is weak, but it is useful as a pressure-sensitive adhesive.

The composition of the present invention is excellent in low die attachability, gives a molded product having no voids, and is suitable for the production of a semiconductor device. A film having a layer obtained from the composition is suitable as a tape for dicing and die bonding.

2 is a DSC chart of the composition prepared in Example 1 and a composition that differs from the composition only in that it does not contain chloroplatinic acid.

Claims (6)

(A) Organopolysiloxane resin represented by the following average composition formula (1), which is solid at normal temperature and has a weight average molecular weight (in terms of styrene) of 400 to 10,000
[Chemical 1]
R ¹ _m R ² _n R ³ _k SiO _{(4-mnk) / 2} (1)

(In Formula (1), R ¹ is a phenyl group, R ³ is an alkenyl group, R ² is a monovalent group excluding a phenyl group and an alkenyl group, and m, k, and n are each 0.45 ≦ m ≦ 2.78, 0 <k ≦ 0.5, 0.2 ≦ n ≦ 2.5, provided that 0.9 ≦ (m + n + k) ≦ 2.8)
(B) Organic peroxide having a half-life of 10 hours and a temperature of 90 ° C or higher
(C) an organohydrogenpolysiloxane having at least two SiH bonds in one molecule, and
(D) In a thermosetting composition comprising an addition reaction catalyst ,
(A) organopolysiloxane resin may have two or more alkenyl groups per molecule, the composition 50% to 99% of the substituents the total number attached to the silicon atom, wherein the Ru der phenyl group . (C) an organohydrogenpolysiloxane, characterized in that contained in an amount of 0.01 to 0.7 mol / mol at a molar ratio to alkenyl groups of the SiH bonds of (A) an organopolysiloxane, wherein Item 2. The composition according to Item 1 . Organic compound containing two or more groups selected from alkenyl group, epoxy group, alkoxysilyl group, acrylic group, methacryl group, ester group, anhydrous carboxy group, isocyanate group, amino group, and amide group in one molecule The composition according to claim 1 or 2, further comprising (E) an adhesion-imparting component selected from the group consisting of an organosilicon compound and an organotitanium compound. The composition according to any one of claims 1 to 3 , further comprising an inorganic filler. A film in which a layer made of the composition according to any one of claims 1 to 4 is formed on at least one surface. The semiconductor device cured product of any one composition according is formed by application of the claims 1-5.

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